Copper-containing azodyestuff



Patented Aug. 8, 1933' COPPER-CONTAINING AzoDYii STUFF Karl Wiedelnann, Leverkusen-I. G. Werk, and

Heinrich Clingestein, Germany, assignors to Inc., New York, N. Y., ware Cologne-on-the-Rhine, General Aniline Works,' a Corporation of Dela No' Drawing. Application December 30, 1931,

Serial No. 584,016, and 1931 infGermany January 9,

5 Claims. (01. 260-12 The present invention relates to new azodye in water in form oftheir-alkali metal saltsand stuffs containing copper, in a complex form, more particularly it relates to dyestuffs which may be' represented by the probable general formula:

wherein R stands for i naphthalene nucleus which may be substituted by an amino group or an acylaminogrouo'such as a-benzoyl-or acetylamino group, the Cu Ogroupb'eing attached to R in o-position to the am group, a:- stands for a carbon-carbon linkage or for the urea bridge -NH,CONH-, y stands for ahydrogen atom or for an acyl group, such as a benzoyl or acetyl group and 'ni-stands for the. numbers'l or 2.

Our new dyestuffs are obtainable by tetrazotizing a diaminodiphenyl or diaminodiphenyl urea containing in o-positionto each diazotiied arnino group an alkoxy group and coupling the result ing tetrazo compound with two mols'oi 2-amino- 5-hydroXynaphthalene-1.7-disulfonic acid or an SOaH N-acyl derivatives thereof--01 with. one mol' of Z-amin'o-(o'r acylamino) 5hydroxynaphthalene- 1.7-disulfonic acid and with one mol of a hydroxynaphthalene-sulfonic acid or an amino (or acylamino) hydroxynaphthalene-sulfonic acid other than Z-amino (or acylamino) -hydroxynapl1tha- 1' lene-1.7-disulfonic acid, and treating the dyegenerally dark metallic, lustrous powders, soluble.

dyeing silk and the cellulosic fibre, such as cotton and viscose, blue to violet shades of excellentfastness tto light. n c r l The invention, is illustrated by the following examples, without being limited thereto:

Example '1.-244 parts by :weight ori -diamino-3.3'-dimethoxydiphenyl are tetrazotized and coupled in a soda-alkaline solution with 758 parts by weight of 2-acetylamino-5-hydroxynaphthalened.7-disulfonic acid. The isolated dyestuff is suspended in 30,000 parts by weight of water free fromlime. The suspension'is acidi I lied, then 500 parts by weight of crystallized copper sulfate, dissolved in 2000 parts by weight of water, are added. Thesuspe'nsion is rendered alkaline bythe addition .of ammonia and heated for 2 hours-at C., thereby maintaining an ammoniacal reaction. The dyestufi having in its free state the probable following formula:

is isolated by the addition of some common salt; in its dry state it is a dark powder, soluble in 3 water with a blue coloration and dyes cotton, silk and. artificial silk of regenerated cellulose reddish blue shades of good fastness to light.

Example 2.-'244 parts by weight of 4.4-'di-. amino-3.3 dimethoxydiphenyl are tetrazotized and coupled in a'weakly-soda-alkaline solution with 319 parts by'weight of'2-amino-5-hydroxynaphthalene-1.T-disulfonic acid, untilthe tetrazo compound can nomore be detected. The diazoazo compound thus formed is combinedina stronger Y soda-alkaline medium with 224 parts by weight of We claim:

1-hydroxynaphthalene-4-su1f0nic acid, and the l. Copper-containing azodystuffs of the probisolated dyestufi is treated, as described in 6X1 able general formula:

ample 1, withi500 parts by weight of crystallized wherein R stands for a naphthalene nucleus copper sulfate. The dyestuff having in its free W ich may be Substitut d y an ammo group 15 state the probable following formula: an acylamino group, the -O Cu O-group (|)...Ou...(l) oulo no I '7 V Hois lhNflz V S0311 V S0311 is soluble in water with a blue coloration and being attached to R in 'o -position to theazo dyes cotton reddish blue shades 'of very good group, a:- stands fora carbon-carbon linkage fastnessto light. i or for a urea bridge, 1/ stands for a hydrogen Example 3.-302 parts by weight of 4.4-di-- atom or for an acyl group and n stands for one amino-33-dimethoxydiphenylurea are tetraof the numbers 1 and 2, being in the free state 5 zotized and coupled in an aqueous sodaalkaline generally metallic, lustrous powders, soluble solution with 758 parts by weight of Z-acetylin water in form of their alkali metal salts and amino-5-hydroxynaphthalene-1.7-disulfonic acid. dyeing silk and the cellulosi-o fibre violet to blue As described in Example 1, the dyestufi is then shades of excellent fa'stness to light. i I

treated with 500 parts by weight of crystallized 2. The Copp azodyestllfi" 0f the 1m copper sulfate. The isolated and dried dyestuff following formula:

O...Cu...0

SOsH 7 l5 i r g having in its free state the probable following being in its free state a dark powder; soluble in formula: I water with a blue coloration and dyeing cotton 0...cu...o O...Ou...0 1 5o l I V N=NC -NH-OONH N=N r V H1 7 SO3 H 7 H038 ir I 7' I 7 0o oo 7 I V 55 l S OaH 0 5 HaC CH:

is soluble in water with a violet coloration and reddish blue shades of very good fastness to dyes cotton bluish-violet shades of very good light. v} -11; fastness to light and ironing. 3. Copper containing azodyestuffs of the prob- The same dyestuff is obtainable by diazotizing able general formula:

O...Ou...(') o...ou.

H\ n Y /H- N V N SOaH HOaS 1 1/ SOsH SOaH J,

1 mol of 5-nitro-2-amino-l-anisol, coupling with wherein a: stands for a carbon-carbon link- 1 mol 2-acetylamino5 -hydroxynaphthalene-1.7- age or for a urea bridge, and 1/ stands forahydisulfonic acid, reducing with sodium sulfide, drogen atom or for an acyl group, being in the phosgenating this aminoazodyestuff' and finally freestategenerally dark metallic, lustrous powcoppering the same. 7 ders; soluble in Water in form oftheir alkali metal salts and dyeing silk and the cellulosic 'fibre violet to blue shades of excellent fastness to light.

4. The copper-containing azodyestufi of the Y, I following form'ula:

\SOIH SOzH v being in its free state a dark powder, soluble in water with'a blue coloration and dyeing cotton, silk and artificial'silk of regenerated cellulose reddish blue shades of good fastness to light.

5. The copper-containing azodystuff of the following formula:

'0...ou...o Y 0...Ou ...0

O som H0|S 4 $03K 1101s H: I

being in its free state a dark powder, soluble in water with a. violet coloration and dyeing cotton bluish-violet shades of very good fastness to light and ironing.

. KARL WIEDEMANN.

HEINRICH CLINGESTEIN. 

